反応 #58698

反応方程式

chloroacetonitrile

Acetonitrile

sodium bis(trimethylsilyl)amide

THF

Chloroacetonitrile

2-Chlorophenyl isothiocyanate

→

title compound

3-Amino-7-(2-chlorophenyl)-6-oxo-6,7-dihydrothieno[2,3-b]pyridine-2-carbonitrile

溶媒

EtOH

反応条件

後処理

1. 1
   その他to give a thick white precipitate
2. 2
   その他to give a brown solution
3. 3
   温度the mixture heated
4. 4
   温度at reflux for 24 h
5. 5
   その他Volatiles were removed in vacuo
6. 6
   workup.DISSOLUTIONthe residue dissolved in acetonitrile (100 mL)
7. 7
   温度the mixture heated at 50° C. for 1 h
8. 8
   workup.ADDITIONwas added
9. 9
   温度heating
10. 10
    その他Some of the acetonitrile (˜50 mL) was removed in vacuo and water
11. 11
    workup.ADDITIONwas added
12. 12
    その他to precipitate the product
13. 13
    ろ過The brown solid was filtered off
14. 14
    洗浄washed with water (50 mL) and Et2O (50 mL)
15. 15
    その他dried

実験手順

Acetonitrile (10 mL) was added to a solution of sodium bis(trimethylsilyl)amide (100 mL, 1.0M in THF, 100 mmol) in THF (50 mL) at −78° C. to give a thick white precipitate. 2-Chlorophenyl isothiocyanate (7.72 g, 45.45 mmol) was added to give a brown solution. The mixture was allowed to warm to r.t. over 1 h then diluted with EtOH (50 mL). N,N-Dimethyluracil (6.4 g, 45 mmol) was added and the mixture heated at reflux for 24 h. Volatiles were removed in vacuo and the residue dissolved in acetonitrile (100 mL). Chloroacetonitrile (2.85 mL, 45 mmol) was added and the mixture heated at 50° C. for 1 h, a second charge of chloroacetonitrile (2.85 mL, 45 mmol) was added and heating continued for 1.5 h. Some of the acetonitrile (˜50 mL) was removed in vacuo and water was added to precipitate the product. The brown solid was filtered off, washed with water (50 mL) and Et2O (50 mL) and dried to give the title compound as a brown solid (14.3 g, quant.). δH (DMSO-d6) 8.10 (1H, d, J 9.7 Hz), 7.75-7.73 (1H, m), 7.65-7.54 (3H, m), 7.14 (2H, br s, NH2), 6.54 (1H, d, J 9.7 Hz). LCMS (ES+) RT 2.97 minutes, 302 (M+H)+.

出典